Organometal compound catalyst

ABSTRACT

This invention is directed to an organometal compound catalyst that is useful for polymerizing at least one monomer to produce a polymer. The catalyst is produced by combining a titanium, zirconium or hafnium organometal compound, preferably a metallocene, at least one organoaluminum compound, and a treated solid oxide. The treated solid oxide compound contains at least one halogen, zirconium and a solid oxide compound.

FIELD OF THE INVENTION

This invention is related to the field of organometal compoundcatalysts.

BACKGROUND OF THE INVENTION

The production of polymers is a multi-billion dollar business. Thisbusiness produces billions of pounds of polymers each year. Millions ofdollars have been spent on developing technologies that can add value tothis business.

One of these technologies is called metallocene catalyst technology.Metallocene catalysts have been known since about 1958. However, theirlow productivity did not allow them to be commercialized. About 1975, itwas discovered that contacting one part water with one parttrimethylaluminum to form methyl aluminoxane, and then contacting suchmethyl aluminoxane with a metallocene compound, formed a metallocenecatalyst that had greater activity. However, it was soon realized thatlarge amounts of expensive methyl aluminoxane were needed to form anactive metallocene catalyst. This has been a significant impediment tothe commercialization of metallocene catalysts.

Fluoro-organo borate compounds have been use in place of large amountsof methyl aluminoxane. However, this is not satisfactory, since suchborate compounds are very sensitive to poisons and decomposition, andcan also be very expensive.

It should also be noted that having a heterogeneous catalyst isimportant. This is because heterogeneous catalysts are required for mostmodern commercial polymerization processes. Furthermore, heterogeneouscatalysts can lead to the formation of substantially uniform polymerparticles that have a high bulk density. These types of substantiallyuniformed particles are desirable because they improve the efficiency ofpolymer production and transportation. Efforts have been made to produceheterogeneous metallocene catalysts; however, these catalysts have notbeen entirely satisfactory.

Therefore, the inventors provide this invention to help solve theseproblems.

SUMMARY OF THE INVENTION

An object of this invention is to provide a process that produces acatalyst composition that can be used to polymerize at least one monomerto produce a polymer.

Another object of this invention is to provide the catalyst composition.

Another object of this invention is to provide a process comprisingcontacting at least one monomer and the catalyst composition underpolymerization conditions to produce the polymer.

Another object of this invention is to provide an article that comprisesthe polymer produced with the catalyst composition of this invention.

In accordance with one embodiment of this invention, a process toproduce a catalyst composition is provided. The process comprises (oroptionally, “consists essentially of”, or “consists of”) contacting anorganometal compound, an organoaluminum compound, and a treated solidoxide compound to produce the catalyst composition,

wherein the organometal compound has the following general formula:

(X¹)(X²)(X³)(X⁴)M¹

wherein M¹ is selected from the group consisting of titanium, zirconium,and hafnium;

wherein (X¹) is independently selected from the group consisting ofcyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls,substituted indenyls, and substituted fluorenyls;

wherein substituents on the substituted cyclopentadienyls, substitutedindenyls, and substituted fluorenyls of (X¹) are selected from the groupconsisting of aliphatic groups, cyclic groups, combinations of aliphaticand cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, germanium, and hydrogen;

wherein at least one substituent on (X¹) can be a bridging group whichconnects (X¹) and (X²);

wherein (X³) and (X⁴) are independently selected from the groupconsisting of halides, aliphatic groups, substituted aliphatic groups,cyclic groups, substituted cyclic groups, combinations of aliphaticgroups and cyclic groups, combinations of substituted aliphatic groupsand cyclic groups, combinations of aliphatic groups and substitutedcyclic groups, combinations of substituted aliphatic groups andsubstituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, and substituted organometallic groups;

wherein (X²) is selected from the group consisting of cyclopentadienyls,indenyls, fluorenyls, substituted cyclopentadienyls, substitutedindenyls, substituted fluorenyls, halides, aliphatic groups, substitutedaliphatic groups, cyclic groups, substituted cyclic groups, combinationsof aliphatic groups and cyclic groups, combinations of substitutedaliphatic groups and cyclic groups, combinations of aliphatic groups andsubstituted cyclic groups, combinations of substituted aliphatic groupsand substituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, and substituted organometallic groups;

wherein substituents on (X²) are selected from the group consisting ofaliphatic groups, cyclic groups, combinations of aliphatic groups andcyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, germanium, and hydrogen;

wherein at least one substituent on (X²) can be a bridging group whichconnects (X¹) and (X²);

wherein the organoaluminum compound has the following general formula:

Al(X⁵)_(n)(X⁶)_(3−n)

wherein (X⁵) is a hydrocarbyl having from 1-20 carbon atoms;

wherein (X⁶) is a halide, hydride, or alkoxide;

wherein “n” is a number from 1 to 3 inclusive; and

wherein the treated solid oxide compound comprises at least one halogen,zirconium, and a solid oxide compound;

wherein the halogen is at least one selected from the group consistingof chlorine, bromine, and fluorine;

wherein the solid oxide compound is selected from the group consistingof alumina, aluminophosphate, aluminosilicate, and mixtures thereof

In accordance with another embodiment of this invention, a process isprovided comprising contacting at least one monomer and the catalystcomposition under polymerization conditions to produce a polymer.

In accordance with another embodiment of this invention, an article isprovided. The article comprises the polymer produced in accordance withthis invention.

These objects, and other objects, will become more apparent to thosewith ordinary skill in the art after reading this disclosure.

DETAILED DESCRIPTION OF THE INVENTION

Organometal compounds used in this invention have the following generalformula:

(X¹)(X²)(X³)(X⁴)M¹

In this formula, M¹ is selected from the group consisting of titanium,zirconium, and hafnium. Currently, it is most preferred when M¹ iszirconium.

In this formula, (X¹) is independently selected from the groupconsisting of (hereafter “Group OMC-I”) cyclopentadienyls, indenyls,fluorenyls, substituted cyclopentadienyls, substituted indenyls, suchas, for example, tetrahydroindenyls, and substituted fluorenyls, suchas, for example, octahydrofluorenyls.

Substituents on the substituted cyclopentadienyls, substituted indenyls,and substituted fluorenyls of (X¹) can be selected independently fromthe group consisting of aliphatic groups, cyclic groups, combinations ofaliphatic and cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, silicon,phosphorus, boron, germanium, and hydrogen, as long as these groups donot substantially, and adversely, affect the polymerization activity ofthe catalyst composition.

Suitable examples of aliphatic groups are hydrocarbyls, such as, forexample, paraffins and olefins. Suitable examples of cyclic groups arecycloparaffins, cycloolefins, cycloacetylenes, and arenes. Substitutedsilyl groups include, but are not limited to, alkylsilyl groups whereeach alkyl group contains from 1 to about 12 carbon atoms, arylsilylgroups, and arylalkylsilyl groups. Suitable alkyl halide groups havealkyl groups with 1 to about 12 carbon atoms. Suitable organometallicgroups include, but are not limited to, substituted silyl derivatives,substituted tin groups, substituted germanium groups, and substitutedboron groups.

Suitable examples of such substituents are methyl, ethyl, propyl, butyl,tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl,nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, phenyl, chloro,bromo, iodo, trimethylsilyl, and phenyloctylsilyl.

In this formula, (X³) and (X⁴) are independently selected from the groupconsisting of (hereafter “Group OMC-II”) halides, aliphatic groups,substituted aliphatic groups, cyclic groups, substituted cyclic groups,combinations of aliphatic groups and cyclic groups, combinations ofsubstituted aliphatic groups and cyclic groups, combinations ofaliphatic groups and substituted cyclic groups, combinations ofsubstituted aliphatic and substituted cyclic groups, amido groups,substituted amido groups, phosphido groups, substituted phosphidogroups, alkyloxide groups, substituted alkyloxide groups, aryloxidegroups, substituted aryloxide groups, organometallic groups, andsubstituted organometallic groups, as long as these groups do notsubstantially, and adversely, affect the polymerization activity of thecatalyst composition.

Suitable examples of aliphatic groups are hydrocarbyls, such as, forexample, paraffins and olefins. Suitable examples of cyclic groups arecycloparaffins, cycloolefins, cycloacetylenes, and arenes. Currently, itis preferred when (X³) and (X⁴) are selected from the group consistingof halides and hydrocarbyls, where such hydrocarbyls have from 1 toabout 10 carbon atoms. However, it is most preferred when (X³) and (X⁴)are selected from the group consisting of fluoro, chloro, and methyl.

In this formula, (X²) can be selected from either Group OMC-I or GroupOMC-II.

At least one substituent on (X¹) or (X²) can be a bridging group thatconnects (X¹) and (X²), as long as the bridging group does notsubstantially, and adversely, affect the activity of the catalystcomposition. Suitable bridging groups include, but are not limited to,aliphatic groups, cyclic groups, combinations of aliphatic groups andcyclic groups, phosphorous groups, nitrogen groups, organometallicgroups, silicon, phosphorus, boron, and germanium.

Suitable examples of aliphatic groups are hydrocarbyls, such as, forexample, paraffins and olefins. Suitable examples of cyclic groups arecycloparaffins, cycloolefins, cycloacetylenes, and arenes. Suitableorganometallic groups include, but are not limited to, substituted silylderivatives, substituted tin groups, substituted germanium groups, andsubstituted boron groups.

Various processes are known to make these organometal compounds. See,for example, U.S. Pat. Nos. 4,939,217; 5,210,352; 5,436,305; 5,401,817;5,631,335, 5,571,880; 5,191,132; 5,480,848; 5,399,636; 5,565,592;5,347,026; 5,594,078; 5,498,581; 5,496,781; 5,563,284; 5,554,795;5,420,320; 5,451,649; 5,541,272; 5,705,478; 5,631,203; 5,654,454;5,705,579; and 5,668,230; the entire disclosures of which are herebyincorporated by reference.

Specific examples of such organometal compounds are as follows:bis(cyclopentadienyl)hafnium dichloride;

bis(cyclopentadienyl)zirconium dichloride;

1,2-ethanediylbis(η⁵-1-indenyl)di-n-butoxyhafnium;

1,2-ethanediylbis(η⁵-1-indenyl)dimethylzirconium;

3,3-pentanediylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride;

methylphenylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride;

bis(n-butylcyclopentadienyl)di-t-butylamidohafnium;

bis(n-butylcyclopentadienyl)zirconium dichloride;

dimethylsilylbis(1-indenyl)zirconium dichloride;

nonyl(phenyl)silylbis(1-indenyl)hafnium dichloride;

dimethylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride;

dimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride;

1,2-ethanediylbis(9-fluorenyl)zirconium dichloride;

indenyl diethoxy titanium(IV) chloride;

(isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride;

bis(pentamethylcyclopentadienyl)zirconium dichloride;

bis(indenyl) zirconium dichloride;

methyloctylsilyl bis (9-fluorenyl) zirconium dichloride;

bis-[1-(N,N-diisopropylamino)boratabenzene]hydridozirconiumtrifluoromethylsulfonate

Preferably, the organometal compound is selected from the groupconsisting of

bis(n-butylcyclopentadienyl)zirconium dichloride;

bis(indenyl)zirconium dichloride;

dimethylsilylbis(1-indenyl) zirconium dichloride;

and

methyloctylsilylbis(9-fluorenyl)zirconium dichloride

Organoaluminum compounds have the following general formula:

Al(X⁵)_(n)(X⁶)_(3−n)

In this formula, (X⁵) is a hydrocarbyl having from 1 to about 20 carbonatoms. Currently, it is preferred when (X⁵) is an alkyl having from 1 toabout 10 carbon atoms. However, it is most preferred when (X⁵) isselected from the group consisting of methyl, ethyl, propyl, butyl, andisobutyl.

In this formula, (X⁶) is a halide, hydride, or alkoxide. Currently, itis preferred when (X⁶) is independently selected from the groupconsisting of fluoro and chloro. However, it is most preferred when (X⁶)is chloro.

In this formula, “n” is a number from 1 to 3 inclusive. However, it ispreferred when “n” is 3.

Examples of such compounds are as follows:

trimethylaluminum;

triethylaluminum (TEA);

tripropylaluminum;

diethylaluminum ethoxide;

tributylaluminum;

diisobutylaluminum hydride;

trisobutylaluminum hydride;

trisobutylaluminum; and

diethylaluminum chloride.

Currently, TEA is preferred.

The treated solid oxide compound comprises at least one halogen,zirconium, and a solid oxide compound. The halogen is at least oneselected from the group consisting of chlorine, bromine, and fluorine.Generally, the solid oxide compound is selected from the groupconsisting of alumina, silica, aluminophosphate, aluminosilicate, andmixtures thereof Preferably, the solid oxide compound is alumina. Thesolid oxide compound can be produced by any method known in the art,such as, for example, by gelling, co-gelling, impregnation of onecompound onto another, and flame hydrolysis.

Generally, the surface area of the solid oxide compound after calciningat 500° C. is from about 100 to about 1000 m²/g, preferably, from about200 to about 800 m²/g, and most preferably, from 250 to 600 m²/g.

The pore volume of the solid oxide compound is typically greater thanabout 0.5 cc/g, preferably, greater than about 0.8 cc/g, and mostpreferably, greater than 1.0 cc/g.

To produce the treated solid oxide compound, at least onezirconium-containing compound is contacted with the solid oxide compoundby any means known in the art to produce a zirconium-containing solidoxide compound. The zirconium can be added to the solid oxide compoundbefore calcining or in a separate step after calcining the solid oxidecompound.

Generally, the solid oxide compound is contacted with an aqueous ororganic solution of the zirconium-containing compound before calcining.For example, the zirconium can be added to the solid oxide compound byforming a slurry of the solid oxide compound in a solution of thezirconium-containing compound and a suitable solvent such as alcohol orwater. Particularly suitable are one to three carbon atom alcoholsbecause of their volatility and low surface tension. A suitable amountof the solution is utilized to provide the desired concentration ofzirconium after drying. Any water soluble or organic soluble zirconiumcompound is suitable that can impregnate the solid oxide compound withzirconium. Examples include, but are not limited to, zirconiumtetrapropoxide, zirconyl nitrate, zirconium acetylacetonate, andmixtures thereof. Drying can be effected by any method known in the art.For example, said drying can be completed by suction filtration followedby evaporation, vacuum drying, spray drying, or flash drying.

If the zirconium is added after calcination, one preferred method is toimpregnate the solid oxide compound with a hydrocarbon solution of azirconium-containing compound, preferably a zirconium alkoxide orhalide, such as, for example, ZrCl₄, Zr(OR)₄, and the like, where R isan alkyl or aryl group having 1 to about 12 carbons. Examples of thezirconium alkoxide include, but are not limited to, zirconiumtetrapropoxide, zirconium tetrabutoxide, and the

Generally, the amount of zirconium present in the zirconium-containingsolid oxide compound is in a range of about 0.1 to about 30 weightpercent zirconium where the weight percent is based on the weight of thezirconium-containing solid oxide compound before calcining or the amountadded to a precalcined solid oxide compound. Preferably, the amount ofzirconium present in the zirconium-containing solid oxide compound is ina range of about 0.5 to about 20 weight percent zirconium based on theweight of the zirconium-containing solid oxide compound before calciningor the amount added to a precalcined solid oxide compound. Mostpreferably, the amount of zirconium present in the zirconium-containingsolid oxide compound is in a range of 1 to 10 weight percent zirconiumbased on the weight of the zirconium-containing solid oxide compoundbefore calcining or the amount added to a precalcined solid oxidecompound.

Before or after the solid oxide compound is combined with thezirconium-containing compound to produce the zirconium-containing solidoxide compound, it is calcined for about 1 minute to about 100 hours,preferably from about 1 hour to about 50 hours, and most preferably,from 3 to 20 hours. Generally, the calcining is conducted at atemperature in a range of about 200° C. to about 900° C., preferablyfrom about 300° C. to about 700° C., and most preferably, from 350° C.to 600° C. The calcining can be conducted in any suitable atmosphere.Generally, the calcining can be completed in an inert atmosphere.Alternatively, the calcining can be completed in an oxidizingatmosphere, such as, oxygen or air, or a reducing atmosphere, such as,hydrogen or carbon monoxide.

After or during calcining, the zirconium-containing solid oxide compoundis contacted with at least one halogen-containing compound. Thehalogen-containing compound is selected from the group consisting ofchlorine-containing compounds, bromine-containing compounds, andfluorine-containing compounds. The halogen-containing compound can be ina liquid phase, or preferably, a vapor phase. Optionally, the solidoxide compound can be calcined at 100 to 900° C. before being contactedwith the halogen-containing compound.

Any method known in the art of contacting the solid oxide compound withthe fluorine-containing compound can be used in this invention. A commonmethod is to impregnate the solid oxide compound with an aqueoussolution of a fluoride-containing salt before calcining, such asammonium fluoride [NH₄F], ammonium bifluoride [NH₄HF₂], hydrofluoricacid [HF], ammonium silicofluoride [(H₄)₂SiF₆], ammonium fluoroborate[NH₄BF₄], ammonium fluorophosphate [NH₄PF₆], and mixtures thereof.

In a second method, the fluorine-containing compound can be dissolvedinto an organic compound, such as an alcohol, and added to the solidoxide compound to minimize shrinkage of pores during drying. Drying canbe accomplished by an method known in the art, such as, for example,vacuum drying, spray drying, flashing drying, and the like.

In a third method, the fluorine-containing compound can be added duringthe calcining step. In this technique, the fluorine-containing compoundis vaporized into the gas stream used to fluidize the solid oxidecompound so that it is fluorided from the gas phase. In addition to someof the fluorine-containing compounds described previously, volatileorganic fluorides may be used at temperatures above their decompositionpoints, or at temperatures high enough to cause reaction. For example,perfluorohexane, perfluorobenzene, trifluoroacetic acid, trifluoroaceticanhydride, hexafluoroacetylacetonate, and mixtures thereof can bevaporized and contacted with the solid oxide compound at about 300 toabout 600° C. in air or nitrogen. Inorganic fluorine-containingcompounds can also be used, such as hydrogen fluoride or even elementalfluorine.

The amount of fluorine on the treated solid oxide compound is about 2 toabout 50 weight percent fluorine based on the weight of the treatedsolid oxide compound before calcining or the amount added to aprecalcined solid oxide compound. Preferably, it is about 3 to about 25weight percent, and most preferably, it is 4 to 20 weight percentfluorine based on the weight of the treated solid oxide compound beforecalcining or the amount added to a precalcined solid oxide compound.

Any method known in the art of contacting the solid oxide compound withthe chlorine-containing compound or bromine-containing compound can beused in this invention. Generally, the contacting is conducted during orafter calcining, preferably during calcining. Any suitablechlorine-containing compound or bromine-containing compound that candeposit chlorine or bromine or both on the solid oxide compound can beused. Suitable chlorine-containing compounds and bromine-containingcompound include volatile or liquid organic chloride or bromidecompounds and inorganic chloride or bromide compounds. Organic chlorideor bromide compounds can be selected from the group consisting of carbontetrachloride, chloroform, dichloroethane, hexachlorobenzene,trichloroacetic acid, bromoform, dibromomethane, perbromopropane,phosgene, and mixtures thereof. Inorganic chloride or bromide compoundscan be selected from the group consisting of gaseous hydrogen chloride,silicon tetrachloride, tin tetrachloride, titanium tetrachloride,aluminum trichloride, boron trichloride, thionyl chloride, sulfurylchloride, hydrogen bromide, boron tribromide, silicon tetrabromide, andmixtures thereof. Additionally, chlorine and bromine gas can be used.Optionally, a fluorine-containing compound can also be included whencontacting the zirconium-containing solid oxide compound with thechlorine-containing compound or bromine-containing compound to achievehigher activity in some cases.

If an inorganic chlorine-containing compound or bromine-containingcompound is used, such as titanium tetrachloride, aluminum trichloride,or boron trichloride, it also can be possible to contact thechlorine-containing compound or bromine-containing compound with thezirconium-containing solid oxide compound after calcining, either byvapor phase deposition or even by using an anhydrous solvent.

The amount of chlorine or bromine used is from about 0.01 to about 10times the weight of the treated solid oxide compound before calcining orthe amount added to a precalcined solid oxide compound, preferably it isfrom about 0.05 to about 5 times, most preferably from 0.05 to 1 timesthe weight of the treated solid oxide compound before calcining or theamount added to a precalcined solid oxide compound.

In another embodiment of this invention, an additional metal other thanzirconium can be added to the treated solid oxide compound to enhancethe activity of the organometal compound. For example, a metal, such as,zinc, silver, copper, antimony, gallium, tin, nickel, tungsten, andmixtures thereof, can be added. This is especially useful if the solidoxide compound is to be chlorided during calcining.

The catalyst compositions of this invention can be produced bycontacting the organometal compound, the organoaluminum compound, andthe treated solid oxide compound, together. This contacting can occur ina variety of ways, such as, for example, blending. Furthermore, each ofthese compounds can be fed into a reactor separately, or variouscombinations of these compounds can be contacted together before beingfurther contacted in the reactor, or all three compounds can becontacted together before being introduced into the reactor.

Currently, one method is to first contact the organometal compound andthe treated solid oxide compound together, for about 1 minute to about24 hours, preferably, 1 minute to 1 hour, at a temperature from about10° C. to about 200° C., preferably 15° C. to 80° C., to form a firstmixture, and then contact this first mixture with an organoaluminumcompound to form the catalyst composition.

Another method is to precontact the organometal compound, theorganoaluminum compound, and the treated solid oxide compound beforeinjection into a polymerization reactor for about 1 minute to about 24hours, preferably, 1 minute to 1 hour, at a temperature from about 10°C. to about 200° C., preferably 20° C. to 80° C.

A weight ratio of the organoaluminum compound to the treated solid oxidecompound in the catalyst composition ranges from about 5:1 to about1:1000, preferably, from about 3:1 to about 1:100, and most preferably,from 1:1 to 1:50.

A weight ratio of the treated solid oxide compound to the organometalcompound in the catalyst composition ranges from about 10,000:1 to about1:1, preferably, from about 1000:1 to about 10:1, and most preferably,from 250:1 to 20:1. These ratios are based on the amount of thecomponents combined to give the catalyst composition.

After contacting, the catalyst composition comprises a post-contactedorganometal compound, a post-contacted organoaluminum compound, and apost-contacted treated solid oxide compound. Preferably, thepost-contacted treated solid oxide compound is the majority, by weight,of the catalyst composition. Often times, specific components of acatalyst are not known, therefore, for this invention, the catalystcomposition is described as comprising post-contacted compounds.

A weight ratio of the post-contacted organoaluminum compound to thepost-contacted treated solid oxide compound in the catalyst compositionranges from about 5:1 to about 1:1000, preferably, from about 3:1 toabout 1:100, and most preferably, from 1:1 to 1:50.

A weight ratio of the post-contacted treated solid oxide compound to thepost-contacted organometal compound in the catalyst composition rangesfrom about 10,000:1 to about 1:1, preferably, from about 1000:1 to about10:1, and most preferably, from 250:1 to 20:1. These ratios are based onthe amount of the components combined to give the catalyst composition.

The catalyst composition of this invention has an activity greater than100 grams of polymer per gram of treated solid oxide compound per hour,preferably greater than 500, and most preferably greater than about1,000. This activity is measured under slurry polymerization conditions,using isobutane as the diluent, and with a polymerization temperature of90° C., and an ethylene pressure of 550 psig. The reactor should havesubstantially no indication of any wall scale, coating or other forms offouling.

One of the important aspects of this invention is that no aluminoxaneneeds to be used in order to form the catalyst composition. Aluminoxaneis an expensive compound that greatly increases polymer productioncosts. This also means that no water is needed to help form suchaluminoxanes. This is beneficial because water can sometimes kill apolymerization process. Additionally, it should be noted that nofluoro-organo borate compounds need to be used in order to form thecatalyst composition. The treated solid oxide compound of this inventionis inorganic when the treated solid oxide compound is formed,heterogenous in a organic polymerization medium, and can be can beeasily and inexpensively produced because of the substantial absence ofany aluminoxane compounds or fluoro-organo borate compounds. It shouldbe noted that organochromium compounds and MgCl₂ are not needed in orderto form the catalyst composition. Although aluminoxane, fluoro-organoborate compounds, organochromium compounds, and MgCl₂ are not needed inthe preferred embodiments, these compounds can be used in otherembodiments of this invention.

In another embodiment of this invention, a process comprising contactingat least one monomer and the catalyst composition to produce a polymeris provided. The term “polymer” as used in this disclosure includeshomopolymers and copolymers. The catalyst composition can be used topolymerize at least one monomer to produce a homopolymer or a copolymer.Usually, homopolymers are comprised of monomer residues, having 2 toabout 20 carbon atoms per molecule, preferably 2 to about 10 carbonatoms per molecule. Currently, it is preferred when at least one monomeris selected from the group consisting of ethylene, propylene, 1-butene,3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, andmixtures thereof.

When a homopolymer is desired, it is most preferred to polymerizeethylene or propylene. When a copolymer is desired, the copolymercomprises monomer residues and one or more comonomer residues, eachhaving from about 2 to about 20 carbon atoms per molecule. Suitablecomonomers include, but are not limited to, aliphatic 1-olefins havingfrom 3 to 20 carbon atoms per molecule, such as, for example, propylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and otherolefins and conjugated or nonconjugated diolefins such as 1,3-butadiene,isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene,1,7-hexadiene, and other such diolefins and mixtures thereof. When acopolymer is desired, it is preferred to polymerize ethylene and atleast one comonomer selected from the group consisting of 1-butene,1-pentene, 1-hexene, 1-octene, and 1-decene. The amount of comonomerintroduced into a reactor zone to produce a copolymer is generally fromabout 0.01 to about 10 weight percent comonomer based on the totalweight of the monomer and comonomer, preferably, about 0.01 to about 5,and most preferably, 0.1 to 4. Alternatively, an amount sufficient togive the above described concentrations, by weight, in the copolymerproduced can be used.

Processes that can polymerize at least one monomer to produce a polymerare known in the art, such as, for example, slurry polymerization, gasphase polymerization, and solution polymerization. It is preferred toperform a slurry polymerization in a loop reaction zone. Suitablediluents used in slurry polymerization are well known in the art andinclude hydrocarbons which are liquid under reaction conditions. Theterm “diluent” as used in this disclosure does not necessarily mean aninert material; it is possible that a diluent can contribute topolymerization. Suitable hydrocarbons include, but are not limited to,cyclohexane, isobutane, n-butane, propane, n-pentane, isopentane,neopentane, and n-hexane. Furthermore, it is most preferred to useisobutane as the diluent in a slurry polymerization. Examples of suchtechnology can be found in U.S. Pat. Nos. 4,424,341; 4,501,885;4,613,484; 4,737,280; and 5,597,892; the entire disclosures of which arehereby incorporated by reference.

The catalyst compositions used in this process produce good qualitypolymer particles without substantially fouling the reactor. When thecatalyst composition is to be used in a loop reactor zone under slurrypolymerization conditions, it is preferred when the particle size of thesolid oxide compound is in the range of about 10 to about 1000 microns,preferably about 25 to about 500 microns, and most preferably, 50 to 200microns, for best control during polymerization.

In a more specific embodiment of this invention, a process is providedto produce a catalyst composition, the process comprising (optionally,“consisting essentially of”, or “consisting of”):

(1) contacting alumina with a solution containing zirconiumtetraalkoxide, (Zr(OR)₄), where R is an aliphatic radical containing oneto twelve carbons, to produce a zirconium-containing alumina having from1 to 10 weight percent zirconium based on the weight of thezirconium-containing alumina before calcining;

(2) calcining the zirconium-containing alumina at a temperature within arange of 350 to 600° C. for 3 to 20 hours to produce a calcinedcomposition;

(3) contacting the calcined composition with carbon tetrachloride in theamount equal to 0.05 to 1 times the weight of the alumina beforecalcining for 10 minutes to 30 minutes to produce a chlorided,zirconium-containing alumina;

(4) combining the chlorided, zirconium-containing alumina andbis(n-butylcyclopentadienyl) zirconium dichloride at a temperaturewithin a range of 15° C. to 80° C. for about 1 minute to 1 hour toproduce a mixture; and

(5) combining the mixture and triethylaluminum to produce the catalystcomposition.

Hydrogen can be used with this invention in a polymerization process tocontrol polymer molecular weight.

A feature of this invention is that the zirconium-containing solid oxidecompound is a polymerization catalyst in it's own right, providing ahigh molecular weight component onto the usually symmetrical molecularweight distribution of the organometal compound. This component, orskewed molecular weight distribution, imparts higher melt strength andshear response to the polymer than could be obtained from an organometalcompound alone. Depending on the relative contributions of thezirconium-containing solid oxide compound and the organometal compound,a bimodal polymer distribution can be obtained.

After the polymers are produced, they can be formed into variousarticles, such as, for example, household containers and utensils, filmproducts, drums, fuel tanks, pipes, geomembranes, and liners. Variousprocesses can form these articles. Usually, additives and modifiers areadded to the polymer in order to provide desired effects. It is believedthat by using the invention described herein, articles can be producedat a lower cost, while maintaining most, if not all, of the uniqueproperties of polymers produced with metallocene catalysts.

EXAMPLES

Testing Methods

A “Quantachrome Autosorb-6 Nitrogen Pore Size Distribution Instrument”was used to determined surface area and pore volume. This instrument wasacquired from the Quantachrome Corporation, Syosset, N.Y.

Melt Index (MI) (g/10 min) was determined using ASTM D1238-95 at 190° C.with a 2,160 gram weight.

High Load Melt Index (HLMI)(g/10 min) was determined using ASTM D1238,Condition E at 190° C. with a 21,600 gram weight.

Solid Oxide Compounds

Silica was obtained from W. R. Grace, grade 952, having a pore volume ofabout 1.6 cc/g and a surface area of about 300 m²/g.

A commercial alumina sold as Ketjen grade B alumina was obtained fromAkzo Nobel Chemical having a pore volume of about 1.78 cc/g and asurface area of about 350 m²/g.

Calcining

To calcine the solid oxide compounds, about 10 grams were placed in a1.75 inch quartz tube fitted with a sintered quartz disk at the bottom.While the solid oxide compound was supported on the disk, dry air wasblown up through the disk at the linear rate of about about 1.6 to about1.8 standard cubic feet per hour. An electric furnace around the quartztube was then turned on, and the temperature was raised at the rate of400° C. per hour to the indicated temperature, such as 600° C. At thattemperature, the solid oxide compound was allowed to fluidize for threehours in the dry air. Afterward, the solid oxide compound was collectedand stored under dry nitrogen, where it was protected from theatmosphere until ready for testing. It was never allowed to experienceany exposure to the atmosphere.

Polymerization Runs

Polymerization runs were made in a 2.2 liter steel reactor equipped witha marine stirrer running at 400 revolutions per minute (rpm). Thereactor was surrounded by a steel jacket containing boiling methanolwith a connection to a steel condenser. The boiling point of themethanol was controlled by varying nitrogen pressure applied to thecondenser and jacket, which permitted precise temperature control towithin half a degree centigrade, with the help of electronic controlinstruments.

A small amount (0.1 to 1.0 grams normally) of a halided solid oxidecompound or inventive treated solid oxide compound was first chargedunder nitrogen to the dry reactor. Next, 2.0 milliliters of a toluenesolution containing 0.5 percent by weight ofbis(n-butylcyclopentadienyl) zirconium dichloride were added, followedby 0.6 liters of isobutane liquid. Then, 1.0 milliliter of a 1.0 molarsolution of triethylaluminum (TEA) was added, followed by another 0.6liters of isobutane liquid. Then, the reactor was heated up to thespecified temperature, typically 90° C., and finally ethylene was addedto the reactor to equal a fixed pressure of 550 psig unless statedotherwise. The reaction mixture was allowed to stir for up to one hour.As ethylene was consumed, more ethylene flowed in to maintain thepressure. The activity was noted by recording the flow of ethylene intothe reactor to maintain the set pressure.

After the allotted time, the ethylene flow was stopped, and the reactorwas slowly depressurized and opened to recover a granular polymer. Inall cases, the reactor was clean with no indication of any wall scale,coating or other forms of fouling. The polymer was then removed andweighed. Activity was specified as grams of polymer produced per gram ofhalided solid oxide compound or treated solid oxide compound charged perhour (g/g/hr).

Description of Result

Specific examples of this invention are described below. The results ofthese polymerization tests are listed in Table 1.

Example 1

1-A (Control—Chlorided Alumina): Ketjen Grade B alumina was calcined indry air at 600° C. for three hours. A sample of this material weighing9.3 grams was heated to 600° C. under dry nitrogen and held at thattemperature another three hours. Then, 2.3 milliliters of carbontetrachloride were injected into the nitrogen stream below the alumina,where it was vaporized and carried up through the alumina bed to producea chlorided alumina. After all of the carbon tetrachloride hadevaporated, the chlorided alumina was cooled to room temperature undernitrogen, then stored in an air-tight glass vessel until used for apolymerization test. When charged to the reactor with an organometalcompound and TEA, it was found to yield an activity of 1066 grams ofpolymer per gram of chlorided alumina per hour. The polymer had a MI of0.17 g/l 0 min, a HLMI of 2.8 g/10 min, and a HLMI/MI ratio of 16.5,reflecting the narrow molecular weight distribution which is typical ofmetallocene produced polymer.

1-B (Control—Chlorided, Zirconium-Containing Alumina): Ketjen Grade Balumina was calcined in dry air at 600° C. for three hours. A sample ofthis material weighing 19.7 grams was impregnated with a solutioncontaining 9.0 milliliters of 80 wt % zirconium tetrabutoxide in butanol(1.049 g/ml) and 31 milliliters of dry heptane to produce azirconium-containing alumina. The excess solvent was evaporated offunder a dry nitrogen flow at about 80° C. The zirconium-containingalumina was then calcined at 500° C. under nitrogen, and during thisprocess, 3.0 milliliters of carbon tetrachloride were injected into thegas stream to produce a chlorided, zirconium-containing alumina. Aftersubstantially all of the carbon tetrachloride had evaporated and passedup through the zirconium-containing alumina bed at 500° C., thechlorided, zirconium-containing alumina was stored under nitrogen.

The chlorided, zirconium-containing alumina was then tested forpolymerization activity with triethylaluminum, but in the absence of anorganometal compound. It yielded 862 grams of polymer per gram ofchlorided, zirconium-containing alumina per hour, demonstrating theinherent activity of the treated solid oxide compound itself. Thepolymer had a MI of zero and a HLMI of zero, indicating the extremelyhigh molecular weight obtained from such zirconium catalysts.

1-C (Inventive—Chlorided, Zirconium-Containing Alumina): The samechlorided, zirconium-containing alumina of Example 1-B was retested forpolymerization activity but in the presence of an organometal compound,as indicated in the procedure described previously. It produced 1484grams of polymer per gram of chlorided, zirconium-containing alumina perhour, indicating the additional contribution of the organometalcompound. Thus, chlorided, zirconium-containing alumina exhibited anactivity comparable to that of the chlorided alumina control in example1-A, however the polymer was much different. The polymer had a MI ofzero and a HLMI of zero, indicating the high molecular weightcontribution from the zirconium.

Example 2

2-A (Control—Chlorided Silica): Davison Grade 952 silica was calcined indry air at 600° C. for three hours. A sample of this material weighingabout 10 grams was heated to 600° C. under dry nitrogen, then 2.3milliliters of carbon tetrachloride were injected into the nitrogenstream below the silica (as in example 1), where it was vaporized andcarried up through the silica bed to produce a chlorided silica. Afterall of the carbon tetrachloride had evaporated, the chlorided silica wascooled to room temperature under nitrogen, then stored in an air-tightglass vessel until used for a polymerization test. When charged to thereactor with an organometal compound and TEA, it was found to produce nopolymer.

2-B (Inventive—Chlorided, Zirconium-Containing Silica): A sample ofDavison grade 952 silica weighing 50 grams was impregnated with 75milliliters of a solution of 80% zirconium butoxide in butanol toproduce a zirconium-containing silica. Then, another 50 milliliters of asolution of 25 milliliters of water and 25 milliliters of propanol wereadded to hydrolyze the zirconium butoxide. This mixture was dried undervacuum for 16 hours at 120° C. A sample of the zirconium-containingsilica weighing 15.90 grams was heated to 600° C. in dry nitrogen for 2hours. Then, 1.0 milliliter of carbon tetrachloride was injected intothe nitrogen flow to chloride the zirconium-containing silica to producea chlorided, zirconium-containing silica. Once substantially all thecarbon tetrachloride had evaporated, the chlorided, zirconium-containingsilica was stored under dry nitrogen.

The chlorided, zirconium-containing silica was then tested forpolymerization activity with triethylaluminum and an organometalcompound as described previously. It yielded 123 grams of polymer pergram of chlorided, zirconium-containing silica per hour. While thisnumber is low, it is a considerable improvement over the chloridedsilica control run in Example 2-A, which yielded no polymer at all. Thisindicates the ability of the chlorided zirconium-containing silica toactivate the organometal compound. Again, this polymer had a MI of zeroand a HLMI of zero, showing the contribution of the zirconium.

2-C (Inventive—Chlorided, Zirconium-Containing Silica): The chlorided,zirconium-containing silica of Example 2-B was tested again forpolymerization activity with an organometal compound andtriethylaluminum, except that 20 psig of hydrogen was also added to thereactor to reduce the molecular weight of the polymer produced. The runproduced a comparable activity, but the molecular weight did notdecrease enough to make much of a change. The MI remained zero, and theHLMI only increased to 0.02. Again, this demonstrates the contributionof the zirconium.

2-D (Inventive—Chlorided, Zirconium-Containing Silica): The chlorided,zirconium-containing silica of Example 2-B was tested again forpolymerization activity with an organometal compound andtriethylaluminum, except that 50 psig of hydrogen was added to thereactor to further reduce the molecular weight of the polymer produced.The run again produced a comparable activity, and the molecular weightdecreased enough to yield a MI of 0.14 and a HLMI of 8.94. This gives abroad molecular weight distribution as indicated by the HLMI/MI ratio of64.8, which is much broader than the organometal compound control inExample 1-A. The broad molecular weight distribution is the result ofcontributions from the organometal compound and the chlorided,zirconium-containing silica.

2-E (Inventive—Chlorided, Zirconium-Containing Silica): The chlorided,zirconium-containing silica of Example 2-B was tested again forpolymerization activity with an organometal compound andtriethylaluminum, adding 50 psig of hydrogen again as in Example 2-D.The run again produced a comparable activity, and the molecular weightdecreased enough to yield a MI of 0.18 and a HLMI of 10.9. This gives abroad molecular weight distribution as indicated by the HLMI/MI ratio of59.6, which is much broader than the organometal compound control inExample 1-A. Again, the broad molecular weight distribution is theresult of contributions from the organometal compound and the chlorided,zirconium-containing silica.

Example 3

3-A (Control—Fluorided Alumina): Ketjen Grade B alumina was calcined indry air at 600° C. for three hours. A sample of the alumina weighing12.3 grams was impregnated with 25 milliliters of an aqueous solutioncontaining 1.25 grams of dissolved ammonium bifluoride and dried in avacuum oven overnight at 120° C. to produce a fluorided alumina. It wasthen heated to 600° C. under dry nitrogen and held at that temperaturefor three hours. The fluorided alumina then was cooled to roomtemperature under nitrogen and stored in an air-tight glass vessel untilused for a polymerization test. When charged to the reactor with anorganometal compound and TEA, it was found to yield an activity of 1250grams of polymer per gram of fluorided alumina per hour. The polymer hada MI of 0.21, a HLMI of 3.48, and a HLMI/MI ratio of 16.6, reflectingthe narrow molecular weight distribution which is typical of metalloceneproduced polymer.

3-B (Control—Fluorided, Zirconium-Containing Alumina): Ketjen Grade Balumina was calcined in dry air at 600° C. for three hours. A sample ofthe alumina weighing 19.7 grams was impregnated with a solutioncontaining 9.0 milliliters of 80 wt % zirconium tetrabutoxide in butanol(1.049 g/ml) and 31 milliliters of dry heptane to produce azirconium-containing alumina. The excess solvent was evaporated offunder a dry nitrogen flow at about 80° C. A sample of thezirconium-containing alumina weighing 16.80 grams was then calcined at600° C. under nitrogen, and during this process 3.0 milliliters ofperfluorohexane were injected into the gas stream to produce afluorided, zirconium-containing alumina. After substantially all of theperfluorohexane had evaporated and passed up through thezirconium-containing alumina bed at 600° C., the gas stream was switchedto dry air for 40 minutes. Finally, the fluorided, zirconium-containingalumina was stored under nitrogen.

The fluorided, zirconium-containing alumina was then tested forpolymerization activity with TEA but in the absence of an organometalcompound. It produced 35 grams of polymer per gram of fluorided,zirconium-containing alumina per hour, indicating that the activity ofthe fluorided, zirconium-containing alumina is much less than theactivity of the chlorided, zirconium-containing alumina in Example 1-B.The polymer obtained had a MI of zero and a HLMI of zero indicating thatthe fluorided, zirconium-containing alumina also produced extremely highmolecular weight polymer.

3-C (Inventive—Fluorided, Zirconium-Containing Alumina): The fluorided,zirconium-containing alumina of Example 3-B was retested forpolymerization activity but this time in the presence of an organometalcompound as described in the polymerization procedure. This time thefluorided, zirconium-containing alumina produced a much higher activityof 1382 grams of polymer per gram of fluorided, zirconium-containingalumina, indicating the ability of the fluorided, zirconium-containingalumina to also activate the organometal compound. The polymer had a MIof zero and a HLMI of 1.74 which is intermediate between the organometalcompound in Example 3-A and the fluorided, zirconium-containing aluminain Example 3-B. Thus, a broader molecular weight distribution wasobtained.

Example 4

4-A (Inventive—Fluorided, Zirconium-Containing Alumina): Ketjen grade Balumina (100-200 mesh, uncalcined) was impregnated with 40 millilitersof a solution made from 20 milliliters of isopropyl alcohol and 24milliliters of an 80 wt % zirconium tetrabutoxide solution in butanol(1.049 g/ml) to produce a zirconium-containing alumina. Thezirconium-containing alumina was dried under vacuum at 120° C.overnight. 11.17 grams of the zirconium-containing alumina were calcinedat 600° C. in dry air for three hours. Then, 5.0 milliliters ofperfluorohexane were injected into the air flow to fluoride thezirconium-containing alumina to produce a fluorided zirconium-containingalumina. Once all of the perfluorohexane had evaporated and passed upthrough the zirconium-containing alumina bed, the fluoridedzirconium-containing alumina was cooled and stored under dry nitrogen.

The fluorided, zirconium-containing alumina was then tested forpolymerization activity with an organometal compound andtriethylaluminum. It produced an activity of 924 grams of polymer pergram of fluorided, zirconium-containing alumina per hour. The polymerhad a MI of 0.03 and a HLMI of 2.26, providing an HLMI/MI ratio of 83.6,which is considerably higher than the pure organometal compound controlin Example 3-A. The higher shear ratio indicates a broader molecularweight distribution, caused by the additional contribution of thefluorided, zirconium-containing alumina. The fluorided,zirconium-containing alumina introduces a small but extremely highmolecular weight polymer component, which accounts for about 4% of theoverall polymer molecular weight distribution in this example.

4-B (Inventive—Fluorided, Zirconium-Containing Alumina): To furtherlower the molecular weight of the polymer obtained, the fluorided,zirconium-containing alumina of Example 4-A was tested again forpolymerization activity with an organometal compound andtriethylaluminum, except that the ethylene pressure was reduced from theusual 550 psig to 450 psig, and 25 milliliters of 1-hexene was alsoadded to make an ethylene-hexene copolymer. Under these conditions, thefluorided, zirconium-containing alumina produced 523 grams of polymerper gram of fluorided, zirconium-containing alumina per hour. Theactivity is lower when compared to Example 4-A due to the lower ethyleneconcentration used. The polymer was found to have a MI of 0.30 and aHLMI of 6.38 giving a HLMI/MI ratio of 21.1. Again, the higher shearratio indicates a broader molecular weight distribution than thatobtained from the organometal compound in Example 3-A due to theadditional contribution of the fluorided, zirconium-containing alumina.The fluorided, zirconium-containing alumina introduces a small butextremely high molecular weight component, which accounts for about 7%of the overall polymer molecular weight distribution in this example.

TABLE 1 Test Polymer MI HLMI Organometal Compound Yield Run TimeActivity (g/10 (g/10 Example Test Compound Compound (g) (g) (minutes)g/g/hr Comments min) min) HLMI/MI 1A Control Cl-Alumina Yes 1.1281 100.25.0 1066 0.17 2.8 16.5 1B Control Cl—Zr/Alumina None 0.4585 247.0 37.5862 0.00 0.00 1C Inventive Cl—Zr/Alumina Yes 0.0874 110.0 50.9 1484 0.000.00 2A Control Cl-Silica Yes 0.4414 0 60.0 0 2B Inventive Cl—Zr/SilicaYes 0.3608 31.3 42.2 123 0.00 0.00 2C Inventive Cl—Zr/Silica Yes 0.282630.6 60.9 107  20 psig H₂ 0.00 0.02 2D Inventive Cl—Zr/Silica Yes 0.413643.5 62.0 102  50 pisg H₂ 0.14 8.94 64.8 2E Inventive Cl—Zr/Silica Yes0.4503 43.2 60.0 96  50 pisg H₂ 0.18 10.90 59.6 3A Control F-Alumina Yes0.2253 281.6 60.0 1250 0.21 3.48 16.6 3B Control F—Zr/Alumina None0.1522 3.0 33.4 35 0.00 0.00 3C Inventive F—Zr/Alumina Yes 0.0832 120.062.6 1382 0.00 1.74 4A Inventive F—Zr/Alumina Yes 0.5510 331.0 39.0 9240.03 2.26 83.6 4B Inventive F—Zr/Alumina Yes 0.0960 50.5 60.3 523 450psig ethylene 0.30 6.38 21.1  25 mls hexene *Activity = grams of polymerper gram of test compound per hour.

While this invention has been described in detail for the purpose ofillustration, it is not intended to be limited thereby but is intendedto cover all changes and modifications within the spirit and scopethereof.

That which is claimed is:
 1. A process to produce a catalystcomposition, said process comprising contacting at least one organometalcompound, at least one organoaluminum compound, and at least one treatedsolid oxide compound to produce said catalyst composition, wherein saidorganometal compound has the following general formula:(X¹)(X²)(X³)(X⁴)M¹ wherein M¹ is selected from the group consisting oftitanium, zirconium, and hafnium; wherein X¹ is selected from the groupconsisting of cyclopentadienyls, indenyls, fluorenyls, substitutedcyclopentadienyls, substituted indenyls, and substituted fluorenyls;wherein substituents on said substituted cylopentadienyls, substitutedindenyls, and substituted fluorenyls of X¹ are selected from the groupconsisting of aliphatic groups, cyclic groups, combinations of aliphaticand cyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, boron groups,and germanium groups; wherein at least one substituent on X¹ isoptionally a bridging group which connects X¹ and X²; wherein X³ and X⁴are independently selected from the group consisting of halides,aliphatic groups, substituted aliphatic groups, cyclic groups,substituted cyclic groups, combinations of aliphatic groups and cyclicgroups, combinations of substituted aliphatic groups and cyclic groups,combinations of aliphatic groups and substituted cyclic groups,combinations of substituted aliphatic groups and substituted cyclicgroups, amido groups, substituted amido groups, phosphido groups,substituted phosphido groups, alkyloxide groups, substituted alkyloxidegroups, aryloxide groups, substituted aryloxide groups, organometallicgroups, and substituted organometallic groups; wherein X² is selectedfrom the group consisting of cyclopentadienyls, indenyls, fluorenyls,substituted cyclopentadienyls, substituted indenyls, substitutedfluorenyls, halides, aliphatic groups, substituted aliphatic groups,cyclic groups, substituted cyclic groups, combinations of aliphaticgroups and cyclic groups, combinations of substituted aliphatic groupsand cyclic groups, combinations of aliphatic groups and substitutedcyclic groups, combinations of substituted aliphatic groups andsubstituted cyclic groups, amido groups, substituted amido groups,phosphido groups, substituted phosphido groups, alkyloxide groups,substituted alkyloxide groups, aryloxide groups, substituted aryloxidegroups, organometallic groups, and substituted organometallic groups;wherein substituents on X² are selected from the group consisting ofaliphatic groups, cyclic groups, combinations of aliphatic groups andcyclic groups, silyl groups, alkyl halide groups, halides,organometallic groups, phosphorus groups, nitrogen groups, boron groups,and germanium groups; wherein at least one substituent on X² isoptionally a bridging group which connects X¹ and X²; wherein saidorganoaluminum compound has the following general formula:Al(X⁵)_(n)(X⁶)_(3−n) wherein X⁵ is a hydrocarbyl having from 1 to about20 carbon atoms; wherein X⁶ is a halide, hydride, or alkoxide; andwherein n is a number from 1 to 3 inclusive; wherein said treated solidoxide compound comprises at least one halogen, zirconium, and a solidoxide compound; wherein said halogen is at least one selected from thegroup consisting of chlorine, bromine, and fluorine; wherein said solidoxide compound is selected from the group consisting of alumina,aluminophosphate, alminosilicate, and mixtures thereof; wherein there isa substantial absence of aluminoxanes.
 2. A process according to claim 1wherein said treated solid oxide compound is contacted with at least oneadditional metal.
 3. A process according to claim 2 wherein said atleast one additional metal is selected from the group consisting ofzinc, silver, copper, antimony, gallium, tin, nickel, tungsten, andmixtures thereof.
 4. A process according to claim 1 wherein said solidoxide compound is calcined at a temperature in a range of about 200° C.to 900° C. and for a time in a range of about 1 minute to about 100hours before or after said solid oxide compound is contacted with azirconium-containing compound.
 5. A process according to claim 4 whereinsaid solid oxide compound is calcined at a temperature in a range ofabout 300° C. to about 700° C. and a time in a range of about 1 hour toabout 50 hours before or after said solid oxide compound is contactedwith a zirconium-containing compound.
 6. A process according to claim 4,wherein said solid oxide compound is calcined at a temperature in arange of 350° C. to 600° C. and a time in a range of 3 hour to 20 hoursbefore or after said solid oxide compound is contacted with azirconium-containing compound.
 7. A process according to claim 1 whereinsaid halogen is added to said solid oxide compound during or aftercalcining.
 8. A process according to claim 1 wherein said organometalcompound, said treated solid oxide compound, and said organoaluminum arecombined by 1) contacting said organometal compound and said treatedsolid oxide compound for about 1 minute to about 24 hours at atemperature from about 10° C. to about 200° C. to form a first mixture;and 2) contacting said first mixture with said organoaluminum compoundto form said catalyst composition.
 9. A process according to claim 8wherein said organometal compound, said treated solid oxide compound,and said organoaluminum are combined by 1) contacting said organometalcompound and said treated solid oxide compound for 1 minute to 1 hour ata temperature from 15° C. to 80° C. to form a first mixture; and 2)contacting said first mixture with said organoaluminum compound to formsaid catalyst composition.
 10. A process according to claim 1 whereinsaid organometal compound, said organoaluminum compound, and saidtreated solid oxide compound are precontacted for 1 minute to 1 hour ata temperature in a range of 20° C. to 80° C.
 11. The process accordingto claim 1 wherein said halogen is chlorine or bromine and the amount ofchlorine or bromine present is in a range of about 0.05 to about 5 timesthe weight of the treated solid oxide compound before calcining or theamount added to a precalcined solid oxide compound.
 12. The processaccording to claim 1 wherein said halogen is fluorine and is present inan amount in a range of about 3 to about 25% by weight, where the weightpercent is based on the weight of said treated solid oxide compoundbefore calcining or the amount added to a precalcined solid oxidecompound.
 13. A process according to claim 1 wherein said treated solidoxide compound is calcined at a temperature in a range of 350° C. to600° C. and a time in a range of 3 hour to 20 hours.
 14. A processaccording to claim 13 wherein said organometal compound, said treatedsolid oxide compound, and said organoaluminum are combined by 1)contacting said organometal compound and said treated solid oxidecompound for 1 minute to 1 hour at a temperature from 15° C. to 80° C.to form a first mixture; and 2) contacting said first mixture with saidorganoaluminum compound to form said catalyst composition.
 15. A processaccording to claim 14 wherein said organometal compound, saidorganoaluminum compound, and said treated solid oxide compound areprecontacted for 1 minute to 1 hour at a temperature in a range of 20°C. to 80° C.
 16. A catalyst composition produced by the process ofclaim
 1. 17. A catalyst composition according to claim 6 wherein saidcatalyst composition has an activity greater than 500 under slurrypolymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and an ethylene pressure of 550psig.
 18. A catalyst composition according to claim 17 wherein saidcatalyst composition has an activity greater than 1000 under slurrypolymerization conditions, using isobutane as a diluent, with apolymerization temperature of 90° C., and an ethylene pressure of 550psig.
 19. A catalyst composition according to claim 17 wherein theweight ratio of said organoaluminum compound to said treated solid oxidecompound in said catalyst composition ranges from about 3:1 to about1:100.
 20. A catalyst composition according to claim 19 wherein saidweight ratio of said organoaluminum compound to said treated solid oxidecompound in said catalyst composition ranges from 1:1 to 1:50.
 21. Acatalyst composition according to claim 17 wherein the weight ratio ofsaid treated solid oxide compound to said organometal compound in saidcatalyst composition ranges from about 1000:1 to about 10:1.
 22. Acatalyst composition according to claim 21 wherein said weight ratio ofsaid treated solid oxide compound to said organometal compound in saidcatalyst composition ranges from 250:1 to 20:1.
 23. A catalystcomposition according to claim 22 wherein said treated solid oxidecompound comprises alumina, 1 to 10 weight percent zirconium per gram ofsaid treated solid oxide compound before calcining, from 4 to 20% weightpercent fluorine based on the weight of said treated solid oxidecompound before calcining, and is calcined for 3 to 20 hours at atemperature from 350 to 600° C.
 24. A catalyst composition according toclaim 16 wherein said solid oxide compound is calcined at a temperaturein a range of about 300° C. to about 700° C. and a time in a range ofabout 1 hour to about 50 hours.
 25. A catalyst composition according toclaim 24 wherein said solid oxide compound is calcined at a temperaturein a range of 350° C. to 600° C. and a time in a range of 3 hours to 20hours.
 26. A catalyst composition according to claim 16 wherein saidsolid oxide compound is alumina.
 27. A catalyst composition according toclaim 16 where the amount of zirconium present in a zirconium-containingsolid oxide compound is in a range of 0.1 to about 30 weight percentzirconium where the weight percent is based on the weight of thezirconium-containing solid oxide compound before calcining or the amountadded to a precalcined solid oxide compound.
 28. A catalyst compositionaccording to claim 16 where the amount of zirconium present in azirconium-containing solid oxide compound is in a range of 0.5 to about20 weight percent zirconium where the weight percent is based on theweight of the zirconium-containing solid oxide compound before calciningor the amount added to a precalcined solid oxide compound.
 29. Acatalyst composition according to claim 16 wherein said halogen isfluorine and is present in an amount in a range of about 3 to about 25%by weight, where the weight percent is based on the weight of saidtreated solid oxide compound before calcining or the amount added to aprecalcined solid oxide compound.
 30. A catalyst composition accordingto claim 16 wherein said halogen is chlorine or bromine and the amountof chlorine or bromine present is in a range of about 0.05 to about 5times the weight of the treated solid oxide compound before calcining orthe amount added to a precalcined solid oxide compound.
 31. A catalystcomposition according to claim 16 wherein said organometal compound isselected from the group consisting of bis(cyclopentadienyl)hafniumdichloride, bis(cyclopentadienyl)zirconium dichloride,1,2-ethanediylbis(η⁵-1-indenyl)di-n-butoxyhafnium,1,2-ethanediylbis(η⁵-1-indenyl)dimethylzirconium,3,3-pentanediylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride,methylphenylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconiumdichloride, bis(n-butylcyclopentadienyl)di-t-butylamido hafnium,bis(n-butylcyclopentadienyl) zirconium dichloride,dimethylsilylbis(1-indenyl) zirconium dichloride,nonyl(phenyl)silylbis(1-indenyl)hafnium dichloride,dimethylsilylbis(η⁵-4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride,dimethylsilylbis(2-methyl-1-indenyl)zirconium dichloride,1,2-ethanediylbis-(9-fluorenyl)zirconium dichloride, indenyl diethoxytitanium(IV) chloride, (isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride, bis(pentamethylcyclopentadienyl)zirconiumdichloride, bis(indenyl)zirconium dichloride,methyloctylsilylbis(9-fluorenyl) zirconium dichloride, andbis-(1-(N,N-diisopropylamino)boratabenzene]hydridozirconiumtrifluoromethylsulfonate.
 32. A catalyst composition according to claim31 wherein said organometal compound is selected from the groupconsisting of bis(n-butylcyclopentadienyl)zirconium dichioride,bis(indenyl)zirconium dichloride, dimethylsilylbis(1-indenyl)zirconiumdichloride, and methyloctylsilylbis(9-fluorenyl)zirconium dichioride.33. A polymerization process comprising contacting at least one monomerand said catalyst composition of claim 16 under polymerizationconditions to produce a polymer.
 34. A process according to claim 33wherein said polymerization conditions comprise slurry polymerizationconditions.
 35. A process according to claim 33 wherein at least onemonomer is ethylene.
 36. A process according to claim 33 wherein atleast one monomer comprises ethylene and an aliphatic 1-olefin having 3to 20 carbon atoms per molecule.
 37. A process according to claim 34wherein said contacting is conducted in a loop reaction zone.
 38. Aprocess according to claim 37 wherein said contacting is conducted inthe presence of a diluent that comprises, in major part, isobutane. 39.A process to produce a catalyst composition being substantially free ofaluminoxanes, said process comprising: (1) contacting alumina with asolution containing a zirconium tetraalkoxide, (Zr(OR)₄), where R is analiphatic radical containing one to twelve carbons, to produce azirconium-containing alumina having from 1 to 10 weight percentzirconium based on the weight of the zirconium-containing alumina beforecalcining; (2) calcining the zirconium-containing alumina at atemperature within a range of 350 to 600° C. for 3 to 20 hours toproduce a calcined composition; (3) contacting the calcined compositionwith carbon tetrachloride in an amount equal to 0.05 to 1 times theweight of the alumina before calcining for 10 minutes to 30 minutes toproduce a chlorided, zirconium-containing alumina; (4) combining thechlorided, zirconium-containing alumina and bis(n-butylcyclopentadienyl)zirconium dichloride at a temperature within a range of 15° C. to 80° C.for about 1 minute to 1 hour to produce a mixture; and (5) combining themixture with triethylaluminum to produce the catalyst composition.
 40. Aprocess according to claim 39 wherein said process consists essentiallyof steps (1), (2), (3), (4), and (5).
 41. A catalyst compositionproduced by the process of claim
 39. 42. A catalyst composition producedby the process of claim
 40. 43. A catalyst composition which issubstantially free of aluminoxanes comprising a post-contactedorganometal compound, a post-contacted organoaluminum compound, and apost-contacted treated solid oxide compound; wherein said treated solidoxide compound comprises at least one halogen, zirconium, and a solidoxide compound; wherein said halogen is selected from the groupconsisting of chlorine, bromine, and fluorine; wherein the solid oxidecompound is selected from the group consisting of alumina,aluminophosphate, aluminosilicate, and mixtures thereof.